CN113138186A - Super-hydrophobic automatic positioning SERS spectrum detection platform and preparation method and application thereof - Google Patents
Super-hydrophobic automatic positioning SERS spectrum detection platform and preparation method and application thereof Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention provides a super-hydrophobic automatic positioning SERS spectrum detection platform and a preparation method and application thereof, and relates to the technical field of Raman spectrum detection. The invention provides a preparation method of a super-hydrophobic automatic positioning SERS spectrum detection platform, which comprises the following steps: arranging an arc-shaped groove on the surface of the substrate; removing the oxide layer on the surface of the arc-shaped groove, and then etching to form a micro-nano structure surface; and evaporating fluorosilane on the surface of the micro-nano structure to obtain the super-hydrophobic automatic positioning SERS spectrum detection platform. The super-hydrophobic automatic positioning SERS spectrum detection platform provided by the invention has the advantages of simple and convenient preparation process, low cost and convenience for practical use; the detection platform provided by the invention is combined with the surface enhanced Raman spectroscopy technology to detect trace analytes, so that the coffee ring effect can be effectively avoided, the detection sensitivity is high, and the stability and the uniformity are good.
Description
Technical Field
The invention relates to the technical field of Raman spectrum detection, in particular to a super-hydrophobic automatic positioning SERS spectrum detection platform and a preparation method and application thereof.
Background
The laser Raman spectrum technology can provide fine structure information and characteristic 'molecular fingerprint' spectrums of molecules, so that the Raman spectrum can identify different molecules, and the Raman spectrum is widely applied to analysis and detection of biochemical molecules, such as qualitative and quantitative analysis of rhodamine, glucose, amino acid, protein, nucleic acid, lipid and other substances. Surface-enhanced Raman spectroscopy (SERS for short) is to enhance the Raman signal of a detection target by means of noble metal nanoparticles (such as gold colloid or silver colloid), so that the autofluorescence signal is effectively inhibited, and the Raman signal intensity can be enhanced by 104～1014The single molecule detection capability can be realized under special conditions, and the method is widely applied to the fields of chemical molecule and biomolecule detection and the like by researchers.
At present, researchers at home and abroad widely use an SERS technology to perform qualitative and quantitative detection on trace analytes in a solution, the detection mainly comprises the steps of mixing an analyte solution with gold colloid or silver colloid, and then dripping the mixture on a substrate without Raman signal background interference to perform SERS detection, and due to the fact that the analytes are randomly distributed on the substrate, the method can hardly detect the analytes with nanomolar and lower concentration. In addition, in blood detection, the method is easy to generate interference of a coffee ring effect, so that molecules in blood cannot be uniformly distributed in each area, and the uniformity and the repeatability of SERS detection are further influenced.
In recent years, super-hydrophobic technology is rapidly started, various super-hydrophobic substrates can concentrate analytes in a small range, SERS detection of molecules in a solution with ultra-low concentration is achieved, and the detection limit can reach the order of attomole magnitude. However, the existing superhydrophobic substrate has the problems of complex process, high cost and the like although the detection sensitivity is extremely high, and mass production and convenient use cannot be realized.
Disclosure of Invention
The invention aims to provide a super-hydrophobic automatic positioning SERS spectrum detection platform and a preparation method and application thereof, and the super-hydrophobic automatic positioning SERS spectrum detection platform provided by the invention is simple and convenient to prepare, low in cost and convenient to use practically; the super-hydrophobic automatic positioning SERS spectrum detection platform provided by the invention is combined with a surface enhanced Raman spectrum technology to detect trace analytes, so that the coffee ring effect can be effectively avoided, and the detection sensitivity is higher.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a super-hydrophobic automatic positioning SERS spectrum detection platform, which comprises the following steps:
arranging an arc-shaped groove on the surface of the substrate;
removing the oxide layer on the surface of the arc-shaped groove, and then etching to form a micro-nano structure surface;
and evaporating fluorosilane on the surface of the micro-nano structure to obtain the super-hydrophobic automatic positioning SERS spectrum detection platform.
Preferably, the fluorosilane comprises trimethoxy (1H, 2H-heptadecafluorodecyl) silane, trimethyl (pentafluoroethyl) silane or triethoxy-1H, 2H-tridecafluoro-n-octyl silane.
Preferably, the number of the arc-shaped grooves is multiple, and the multiple arc-shaped grooves are arranged in an array.
Preferably, the evaporation temperature is 80-120 ℃; the time of evaporation is 1-3 h.
The invention also provides a super-hydrophobic automatic positioning SERS spectrum detection platform prepared by the preparation method in the technical scheme, which comprises a substrate and a super-hydrophobic arc-shaped groove arranged on the surface of the substrate, wherein the contact angle of the super-hydrophobic arc-shaped groove is 153-163 degrees.
The invention also provides application of the super-hydrophobic automatic positioning SERS spectrum detection platform in surface enhanced Raman spectrum detection.
The invention provides a surface enhanced Raman spectroscopy detection method, which comprises the following steps:
and mixing the noble metal nano sol with the analyte sample solution, dropwise adding the obtained mixed solution into the super-hydrophobic arc-shaped groove of the super-hydrophobic automatic positioning SERS spectrum detection platform in the technical scheme, and performing surface enhanced Raman spectrum detection after sequentially incubating and drying.
Preferably, the analyte sample in the analyte sample solution comprises an environmental contaminant or a biomarker.
Preferably, the noble metal nanosol comprises a silver nanosol or a gold nanosol.
Preferably, the volume ratio of the noble metal nano sol to the analyte sample solution is 1-5: 1; the concentration of the noble metal nano sol is 100-600 nmol/L; the concentration of the analyte sample solution is greater than 10-13mol/L。
The invention provides a preparation method of a super-hydrophobic automatic positioning SERS spectrum detection platform, which comprises the following steps: arranging an arc-shaped groove on the surface of the substrate; removing the oxide layer on the surface of the arc-shaped groove, and then etching to form a micro-nano structure surface; and evaporating fluorosilane on the surface of the micro-nano structure to obtain the super-hydrophobic automatic positioning SERS spectrum detection platform. In the invention, the groove is arranged in an arc shape, so that an analyte sample and noble metal nano sol can be gathered at the bottom and automatically positioned at one point, and the detection sensitivity is improved; the oxide layer on the surface of the arc-shaped groove is removed, so that the roughness of the surface of the substrate can be increased; then etching the surface of the arc-shaped groove into a micro-nano structure, increasing the contact area of the surface of the arc-shaped groove and air, causing a constant contact angle evaporation mode, and promoting the concentration of an analyte sample; the fluoro-silane is evaporated on the surface of the micro-nano structure, so that an arc-shaped groove with a super-hydrophobic effect can be obtained; because the arc-shaped groove has a super-hydrophobic effect, the mixed solution of the analyte sample solution and the noble metal nano sol can automatically slide to the central position of the bottom of the arc-shaped groove under the action of gravity, so that the automatic positioning function is realized, and the surface enhanced Raman spectroscopy high-throughput detection is facilitated. The super-hydrophobic automatic positioning SERS spectrum detection platform provided by the invention is simple and convenient to prepare, low in cost and convenient to use practically.
The super-hydrophobic automatic positioning SERS spectrum detection platform provided by the invention is combined with a surface enhanced Raman spectrum technology to detect trace analytes, so that the coffee ring effect can be effectively avoided, the detection sensitivity is high, and the stability, the uniformity and the reproducibility are good. By combining the super-hydrophobic automatic positioning SERS spectrum detection platform provided by the invention with noble metal nano sol and surface enhanced Raman spectroscopy technology, high-throughput and automatic detection of a large batch of samples can be realized.
Drawings
FIG. 1 is a schematic diagram of a preparation method of a super-hydrophobic automatic positioning SERS spectrum detection platform according to the present invention;
FIG. 2 is a diagram of a super-hydrophobic automatic positioning SERS spectrum detection platform prepared in example 1;
FIG. 3 is a graph comparing contact angles of untreated aluminum plates and super-hydrophobic arc-shaped grooves on which water is dripped;
FIG. 4 is a transmission electron microscope image of silver nanosol in application example 1;
FIG. 5 is a diagram of rhodamine SERS spectra for different concentration gradients in application example 1;
FIG. 6 shows that the rhodamine spectrum in application example 1 is located at 612cm-1A quantitative standard curve of peak intensity versus concentration;
FIG. 7 is a SERS spectrum of tryptophan, glucose and adenine in application example 2;
FIG. 8 is a comparison graph of the serum sample and the silver nanosol mixed solution of application example 3 after being dried by being dropped on an untreated aluminum sheet (the middle position of the second row) and in a super-hydrophobic arc-shaped groove;
FIG. 9 is a graph showing the SERS spectra obtained by dropping the serum sample and the silver nanosol mixed solution on an untreated aluminum sheet and in a super-hydrophobic arc-shaped groove in application example 3.
Detailed Description
The invention provides a preparation method of a super-hydrophobic automatic positioning SERS spectrum detection platform, which comprises the following steps:
arranging an arc-shaped groove on the surface of the substrate;
removing the oxide layer on the surface of the arc-shaped groove, and then etching to form a micro-nano structure surface;
and evaporating fluorosilane on the surface of the micro-nano structure to obtain the super-hydrophobic automatic positioning SERS spectrum detection platform.
The invention provides a circular arc groove arranged on the surface of a substrate. In the present invention, the substrate is preferably an aluminum plate. The size of the aluminum plate is not required to be specially selected according to actual requirements. In a specific embodiment of the invention, the thickness of the aluminum plate is preferably 2-15 mm, and more preferably 8 mm; the length x width x height of the aluminum plate is preferably 171mm x 8 mm.
The method for arranging the plurality of circular arc-shaped grooves on the surface of the substrate is preferably to drill grooves. In the present invention, the method of drilling a slot preferably comprises: and (4) carrying out face smoothing on the substrate, and then drilling a groove at a fixed point in a patterned paper mode. In the present invention, it is preferable to perform surface smoothing of the aluminum plate by using a high-precision numerically controlled machine tool.
In the present invention, the number of the circular arc grooves is preferably a plurality, and more preferably 100; the plurality of circular arc-shaped grooves are preferably arranged in an array. The invention has no special requirement on the specific size of the arc-shaped groove and can be determined according to the actual requirement. In a specific embodiment of the invention, the arc of the circular arc-shaped groove is preferably pi/9 to pi/2, more preferably 9.1 pi/20. In a specific embodiment of the invention, the opening diameter of the circular arc-shaped groove is 8mm, the depth of the circular arc-shaped groove is 1.5mm, the circular arc-shaped groove is in a half arc shape, and the center distance between two adjacent circular arc-shaped grooves is 16 mm.
After the arc-shaped groove is obtained, the oxide layer on the surface of the arc-shaped groove is removed, and then etching is carried out, so that the micro-nano structure surface is formed. In the present invention, the method for removing the oxide layer on the surface of the circular arc-shaped groove is preferably grinding. In the present invention, the method of polishing preferably comprises: and (3) polishing the surface of the circular arc-shaped groove by using sand paper, and then cleaning and drying. In the invention, the type of the sand paper is preferably 300-6000 meshes, and more preferably 1200 meshes; the grinding time of each circular arc groove is preferably 10 s. In the present invention, the washing preferably includes water washing, acetone washing, and ethanol washing, which are sequentially performed. In the present invention, the water washing is preferably an ultra-pure water washing; the ethanol washing is preferably absolute ethanol washing; the water washing, acetone washing and ethanol washing are independently and preferably carried out under the ultrasonic condition; the time for washing with water, acetone and ethanol is preferably 5-10 min independently. The invention has no special requirements on the specific process parameters of the drying, and the drying method known by the technical personnel in the field can be adopted.
The invention etches the polished circular arc-shaped groove. In the present invention, the method of etching preferably includes: and dropwise adding etching liquid on the surface of the polished circular arc groove for etching. In the invention, the etching solution adopted by the etching preferably comprises hydrochloric acid solution; the concentration of the hydrochloric acid solution is preferably 2-5 mol/L, and more preferably 3-4 mol/L. In the invention, the etching time is preferably 3-24 hours, and more preferably 3-5 hours. In the specific embodiment of the invention, when the opening diameter of the circular arc-shaped groove is 8mm, the depth is 1.5mm, and the radian is 9.1 pi/20, the dosage of the hydrochloric acid solution is preferably 45-90 μ L.
In the invention, after the etching, the obtained arc-shaped groove is preferably subjected to post-treatment to obtain the arc-shaped groove with the micro-nano structure surface. In the present invention, the post-treatment preferably includes washing and drying which are performed in this order. In the present invention, the washing preferably includes water washing and ethanol washing performed in this order. In the present invention, the water washing is preferably an ultra-pure water washing; the ethanol washing is preferably absolute ethanol washing; the water washing and the ethanol washing are independently preferably carried out under the ultrasonic condition; the time for washing with water and the time for washing with ethanol are preferably 5-10 min independently. The invention has no special requirements on the specific process parameters of the drying, and the drying method known by the technical personnel in the field can be adopted.
According to the invention, fluorosilane is evaporated on the surface of the micro-nano structure to obtain the super-hydrophobic automatic positioning SERS spectrum detection platform. In the present invention, the fluorosilane preferably includes trimethoxy (1H,1H,2H, 2H-heptadecafluorodecyl) silane, trimethyl (pentafluoroethyl) silane, or triethoxy-1H, 1H,2H, 2H-tridecafluoro-n-octyl silane. According to the invention, the arc-shaped groove is etched to form a micro-nano structure, and the surface of the arc-shaped groove has a super-hydrophobic effect by combining with fluorosilane.
In the present invention, the method for vapor deposition preferably includes: and placing the fluorosilane and the substrate in a closed container for evaporation. In a specific embodiment of the invention, when the opening diameter of the circular arc-shaped groove is 8mm, the depth is 1.5mm, and the radian is 9.1 pi/20, the usage amount of the fluorosilane is preferably 0.1-0.7 mL, and more preferably 0.5 mL. In the invention, the evaporation temperature is preferably 80-120 ℃, and more preferably 90 ℃; the time for vapor deposition is preferably 1 to 3 hours, and more preferably 2 hours. In the present invention, the closed container is preferably a closed glass dish or a closed stainless steel box.
In the present invention, it is preferable that the vapor deposition is performed at room temperature, and a vapor deposition layer is formed on the surface of the arc-shaped groove. In the present invention, the vapor deposition layer on the surface of the circular arc-shaped groove is preferably a monomolecular layer.
In a specific embodiment of the invention, the preparation method of the super-hydrophobic automatic positioning SERS spectrum detection platform is shown in fig. 1, an aluminum plate is subjected to groove drilling, sand paper polishing, hydrochloric acid etching and fluorosilane modification by a digital control machine tool to form super-hydrophobic circular arc-shaped grooves arranged in an array, a mixed solution of an analyte and silver nano sol is dried and then concentrated into a small and uniformly distributed point, the point is automatically positioned to the center of the bottom of the circular arc-shaped groove, and then the efficient and reproducible analyte surface enhanced raman spectrum detection is performed.
The invention also provides a super-hydrophobic automatic positioning SERS spectrum detection platform prepared by the preparation method in the technical scheme, which comprises a substrate and a super-hydrophobic arc-shaped groove arranged on the surface of the substrate, wherein the contact angle of the super-hydrophobic arc-shaped groove is 153-163 degrees, and preferably 158 degrees. In the invention, the super-hydrophobic arc-shaped groove comprises an arc-shaped groove and a vapor deposition layer arranged on the surface of the arc-shaped groove, and the vapor deposition layer comprises fluorosilane molecules.
The invention also provides application of the super-hydrophobic automatic positioning SERS spectrum detection platform in surface enhanced Raman spectrum detection, and the super-hydrophobic automatic positioning SERS spectrum detection platform is particularly suitable for surface enhanced Raman spectrum detection of trace and trace analytes.
The invention also provides a surface enhanced Raman spectroscopy detection method, which comprises the following steps:
and mixing the noble metal nano sol with the analyte sample solution, dropwise adding the obtained mixed solution into the super-hydrophobic arc-shaped groove of the super-hydrophobic automatic positioning SERS spectrum detection platform in the technical scheme, and performing surface enhanced Raman spectrum detection after sequentially incubating and drying.
In the present invention, the noble metal nanosol preferably includes silver nanosol or gold nanosol, and more preferably silver nanosol. In the invention, the concentration of the noble metal nano sol is preferably 100-600 nmol/L, and more preferably 300-500 nmol/L. In a specific embodiment of the invention, the concentration of the nano silver in the silver nano sol is preferably 300nmol/L, and the particle size of the nano silver in the silver nano sol is 45-50 nm.
In a specific embodiment of the present invention, the method for preparing the silver nanosol preferably comprises the steps of: mixing the silver nitrate solution, the sodium hydroxide solution and the reducing agent solution, and centrifuging the obtained mixed solution to obtain the silver nano sol. In the invention, the concentration of the silver nitrate solution is preferably 0.15-0.20 mg/mL, and more preferably 0.19 mg/mL; the concentration of the sodium hydroxide solution is preferably 0.05-0.2 mol/L, and more preferably 0.1 mol/L; the reducing agent solution is preferably hydroxylamine hydrochloride solution or sodium citrate solution; the concentration of the reducing agent solution is preferably 0.01-0.2 mol/L, and more preferably 0.06 mol/L. In the present invention, the volume ratio of the silver nitrate solution, the sodium hydroxide solution and the reducing agent solution is preferably 20:1: 1.
In the present invention, the method of mixing the silver nitrate solution, the sodium hydroxide solution, and the reducing agent solution is preferably: mixing a sodium hydroxide solution and a reducing agent solution to obtain a mixed solution; and adding the mixed solution into a silver nitrate solution, and stirring. In the invention, the stirring speed is preferably 100-1500 r/min, and more preferably 800 r/min. The stirring time is not specially required, and the uniform milk gray solution is preferably obtained.
In the invention, the centrifugal speed is preferably 4000-12000 r/min, more preferably 10000 r/min; the time for centrifugation is preferably 6-15 min, and more preferably 10 min. The invention leads the silver colloid to be layered by centrifugation, and the supernatant fluid is discarded, and the lower layer concentrate is the silver nanometer sol.
In the present invention, the analyte sample in the analyte sample solution preferably comprises an environmental contaminant or a biomarker; the environmental pollutants preferably comprise rhodamine, methyl blue or pesticide residue small molecules; the biomarker preferably comprises tryptophan, glucose or adenine. In the present invention, the solvent of the analyte sample solution is preferably ultrapure water or a solvent having a surface energy greater than water. In the present invention, the concentration of the analyte sample solution is preferably greater than 10-13mol/L, more preferably 10-3～10-12mol/L, more preferably 10-7mol/L. In a particular embodiment of the invention, the analyte sample solution preferably comprises a human body fluid, particularly preferably serum, urine, saliva or tears.
In the invention, the volume ratio of the noble metal nano sol to the analyte sample solution is preferably 1-5: 1, and more preferably 5: 1. The present invention has no special requirements for the mixing method of the noble metal nano sol and the analyte sample solution, and the mixing method known to those skilled in the art can be adopted.
In the invention, the dripping amount of the mixed solution of the noble metal nano-sol and the analyte sample solution on the super-hydrophobic automatic positioning SERS spectrum detection platform is preferably 2-50 muL, and more preferably 12 muL.
In the present invention, the incubation temperature is preferably normal temperature, and the incubation manner is preferably standing; the incubation time is preferably 5-60 min, and more preferably 20 min. According to the invention, the noble metal nano sol and the analyte sample solution are uniformly mixed through incubation. In the invention, the drying temperature is preferably 15-40 ℃, and more preferably 25 ℃; the drying time is preferably 20-60 min, and more preferably 20 min. In the drying process, the noble metal nano sol and the analyte sample solution can be automatically and uniformly mixed and concentrated to a very small point, the problem of uneven distribution of SERS spectral signals caused by coffee ring effect can be solved, and the SERS spectral signals with stable reproducibility can be obtained. In a specific embodiment of the present invention, after the drying, the noble metal nanosol and the analyte sample are concentrated to a point having a diameter of 0.5 to 1 mm.
In the present invention, the conditions for the surface enhanced raman spectroscopy detection preferably include: x50 times mirror; the laser wavelength is 785 nm; integration time 10 s; the exciting light power is 10 mW; the spectral range is 400-1800 cm-1。
Preferably, after the surface-enhanced raman spectroscopy detection is performed, the obtained surface-enhanced raman spectroscopy original data is subjected to fluorescence background subtraction data preprocessing to obtain surface-enhanced raman spectroscopy detection data of the analyte sample. The invention has no special requirements on the specific method for preprocessing the fluorescence background subtraction data, and adopts the method well known by the technical personnel in the field, and the invention preferably utilizes polynomial fitting to subtract the fluorescence background of the obtained surface enhanced Raman spectrum original data.
The invention can perform qualitative or quantitative analysis on the analyte sample according to the surface enhanced Raman spectroscopy detection data of the analyte sample. Specifically, the qualitative analysis is carried out according to the intensity of a characteristic peak in a surface enhanced Raman spectrum of an analyte sample; or, firstly, carrying out surface enhanced Raman spectroscopy detection on the standard sample to obtain a standard curve; and then determining the concentration of the analyte sample according to the surface enhanced Raman spectroscopy detection data of the analyte sample, thereby realizing the quantitative analysis of the analyte sample.
In the invention, the detection range of the noble metal nano sol and the rhodamine solution after being dried in the super-hydrophobic arc-shaped groove is preferably 10-9～10-12mol/L, detection limit is lower than 10-12mol/L. In the present invention, when the analyte sample in the analyte sample solution is tryptophan, glucose or adenine, the detection limit is less than 10-7mol/L。
The surface-enhanced Raman spectrum detection method provided by the invention can overcome the coffee ring effect, can realize rapid positioning of the analyte, and can detect the analyte stably, with high flux and high sensitivity.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
An aluminum plate with the length multiplied by the width multiplied by the height multiplied by 171mm multiplied by 8mm is placed on a numerical control machine tool with set parameters to drill grooves, the total number of the grooves is 100 arc-shaped grooves, the opening diameter of each arc-shaped groove is 8mm, the depth is 1.5mm, the shape is a half arc shape, and the central distance between two adjacent arc-shaped grooves is 16 mm;
polishing each arc-shaped groove on the aluminum plate for 10s by using 1200# abrasive paper, and then sequentially ultrasonically cleaning the aluminum plate by using ultrapure water, acetone and absolute ethyl alcohol for 10 min; adding 70 mu L of 3mol/L HCl solution into each cleaned circular arc-shaped groove, etching for 3h, sequentially and independently ultrasonically cleaning for 10min by using ultrapure water and absolute ethyl alcohol, and drying at room temperature (25 ℃); and then placing the etched aluminum plate and 0.5mL of trimethoxy (1H,1H,2H, 2H-heptadecafluorodecyl) silane in a closed stainless steel box together, placing the box in a forced air drying box, evaporating at 120 ℃ for 120min, and finally cooling at room temperature, wherein each circular arc groove has super-hydrophobic performance, the contact angle is 158 degrees, and super-hydrophobic circular arc grooves are formed, so that the super-hydrophobic automatic positioning SERS spectrum detection platform is obtained.
The real object diagram of the super-hydrophobic automatic positioning SERS spectrum detection platform prepared in the embodiment is shown in FIG. 2, and a circular arc groove in the right side diagram in FIG. 2 is sequentially filled with rhodamine solution, water, gold nano sol and silver nano sol from left to right. As can be seen from FIG. 2, the circular arc-shaped groove of the super-hydrophobic automatic positioning SERS spectrum detection platform prepared by the invention has a super-hydrophobic effect.
The contact angle of dropping water on an untreated aluminum plate is shown in fig. 3 (a); the contact angle diagram of water dropped on the super-hydrophobic arc-shaped groove prepared by the invention is shown as (B) in figure 3. As can be seen from FIG. 3, the contact angle of the super-hydrophobic circular arc-shaped groove prepared by the method is 158 degrees, and the super-hydrophobic circular arc-shaped groove has super-hydrophobic performance.
Application example 1
(1) Synthesis of silver nano sol:
into the conical flask, 90mL of ultrapure water and 0.017gAgNO were added3Stirring and dissolving to obtain silver nitrate solution; uniformly mixing 4.5mL of sodium hydroxide solution (0.1mol) and 5mL of hydroxylamine hydrochloride solution (0.06mol), quickly adding into the conical flask, and uniformly stirring until a uniform milk gray solution is obtained; centrifuging for 10 minutes at 10000r/min by using a centrifuge to layer the silver colloid, discarding the supernatant, and taking the lower concentrated silver nano sol and sealing for later use at room temperature in a dark place; the concentration of the silver nano sol is 300 nmol/L.
The transmission electron microscope image of the silver nano sol is shown in fig. 4, and the particle size of nano silver in the silver nano sol is 45 nm.
(2) The super-hydrophobic automatic positioning SERS spectrum detection platform prepared in the embodiment 1 is utilized to detect rhodamine:
taking 10 μ L of 10-9mol/L、10-10mol/L、10-11mol/L、10-12And (2) mixing the mol/L of four rhodamine standard solutions with different concentration gradients with 2 mu L of the silver nano sol obtained in the step (1), dropwise adding the obtained mixed solution into the super-hydrophobic arc-shaped groove of the super-hydrophobic automatic positioning SERS spectrum detection platform prepared in the embodiment 1, sequentially performing room-temperature incubation for 20min and drying (at the temperature of 25 ℃) for 20min, and performing SERS detection to obtain rhodamine SERS spectra with different concentration gradients. Wherein, the SERS detection conditions comprise: x50 times mirror; the laser wavelength is 785 nm; integration time 10 s; the exciting light power is 10 mW; the spectral range is 400-1800 cm-1。
The obtained rhodamine SERS spectra with different concentration gradients are shown in FIG. 5 and are arranged at 612cm-1The intensity of (c) was plotted for quantitative analysis as shown in fig. 6. As can be seen from FIGS. 5 to 6, the detection platform has good linear correlation when used for detecting rhodamine with different concentration gradients, and the detection sensitivity can reach 10-12The mol/L result shows that the super-hydrophobic self-positioning SERS spectrum detection platform prepared by the invention has super-sensitive detection efficiency on small molecular substances.
Application example 2
According to the detection method of application example 1, 10-7mixing a tryptophan solution, a glucose solution and an adenine solution in mol/L with 2 mu L of silver nano sol, dropwise adding the obtained mixed solution into a super-hydrophobic arc-shaped groove of the super-hydrophobic automatic positioning SERS spectrum detection platform prepared in the embodiment 1, sequentially performing room-temperature incubation for 20min and drying (at 25 ℃) for 20min, and performing SERS detection to obtain SERS spectra of tryptophan, glucose and adenine, wherein the SERS spectra are shown in FIG. 7. Wherein, the SERS detection conditions comprise: x50 times mirror; the laser wavelength is 785 nm; integration time 10 s; the exciting light power is 10 mW; the spectral range is 400-1800 cm-1。
Application example 3
Collecting a serum sample:
the serum sample is provided by Fujian tumor hospital, and the overnight fasting blood of the person between 7 and 8 am is extracted under aseptic condition, centrifuged at 2000r/min for 15min, and the upper serum is taken as the serum sample.
Serum sample SERS detection:
adding 10 mu L of serum sample into a test tube subjected to sterile disinfection treatment by using a pipette; and adding 10 mu L of silver nano sol into the test tube by using a pipette, mixing the serum sample and the silver nano sol according to the volume ratio of 1:1, fully stirring the obtained mixed solution to uniformly mix the serum sample and the silver nano sol, respectively dropwise adding all the prepared mixed solution onto an untreated aluminum sheet and into the super-hydrophobic circular arc-shaped groove of the super-hydrophobic automatic positioning SERS spectrum detection platform prepared in the embodiment 1, wherein the mixed solution slides to the central part of the bottom of the super-hydrophobic circular arc-shaped groove in a spherical manner due to the super-hydrophobic performance of the super-hydrophobic circular arc-shaped groove, incubating and drying at normal temperature, and then randomly collecting 5 serum surface enhanced Raman spectra on each sample. Wherein, the SERS detection conditions comprise: x50 times mirror; the laser wavelength is 785 nm; integration time 10 s; the exciting light power is 10 mW; the spectral range is 400-1800 cm-1。
FIG. 8 is a comparison of the serum sample and the mixed solution of silver nanosol dripped onto an untreated aluminum sheet (middle position of the second row) and dried in a super-hydrophobic arc-shaped groove. As can be seen from fig. 8, the area of the serum sample after incubation and drying on the untreated aluminum sheet is much larger than that in the superhydrophobic circular arc-shaped groove, which indicates that the superhydrophobic circular arc-shaped groove of the invention has the effect of concentrating the sample.
Fig. 9 (a) is a picture of a serum sample and a silver nanosol mixed solution dropped on an untreated aluminum plate under a microscope and dried, and it can be seen from fig. 9 (a) that the serum sample has a non-uniform surface and a distinct coffee ring; fig. 9 (B) is a picture of a serum sample and a silver nanosol mixed solution dropwise added in a super-hydrophobic arc-shaped groove under a microscope and dried, and it can be seen from fig. 9 (B) that the surface of the serum sample is uniform and has no obvious coffee ring; fig. 9(C) is 5 SERS spectra corresponding to 5 positions in (a); fig. 9 (D) shows 5 SERS spectra corresponding to 5 positions in (B). As can be seen from (C) and (D) in fig. 9, there is a difference between the 5 SERS spectra obtained from the sample on the untreated aluminum plate, and a SERS spectrum with a high signal-to-noise ratio can only be obtained on the coffee ring (as shown in 1 in fig. 9 (C)), and the signal-to-noise ratio of the SERS spectrum not measured on the coffee ring is very poor, and there is a difference between the peak positions and intensities of the five SERS spectra. Therefore, it takes more time to find the best test point using an untreated aluminum plate as a substrate. However, the SERS spectra of 5 serum samples obtained in the super-hydrophobic circular arc-shaped grooves have very good signal-to-noise ratio and very good reproducibility among the spectra. Therefore, the results show that the super-hydrophobic arc-shaped groove can efficiently collect the sample, avoid the coffee ring effect and contribute to quickly collecting the SERS spectrum of the sample.
The invention obtains high-quality SERS spectrum signals of the analyte by utilizing an SERS spectrum measuring method, realizes quick and lossless quantitative detection and identification according to the intensity of the spectrum peak of the SERS spectrum of the analyte, and proves that the stability and the uniformity of the SERS spectrum of the serum are improved by utilizing the super-hydrophobic automatic positioning SERS spectrum detection platform in the serum detection. Therefore, the super-hydrophobic automatic positioning SERS spectrum detection platform constructed by the invention has huge potential in the aspect of high-precision detection of trace analytes, and provides a reliable auxiliary method for SERS detection of ultra-trace small molecule analytes and serum.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a super-hydrophobic automatic positioning SERS spectrum detection platform comprises the following steps:
arranging an arc-shaped groove on the surface of the substrate;
removing the oxide layer on the surface of the arc-shaped groove, and then etching to form a micro-nano structure surface;
and evaporating fluorosilane on the surface of the micro-nano structure to obtain the super-hydrophobic automatic positioning SERS spectrum detection platform.
2. The method according to claim 1, wherein the fluorosilane comprises trimethoxy (1H,1H,2H, 2H-heptadecafluorodecyl) silane, trimethyl (pentafluoroethyl) silane, or triethoxy-1H, 1H,2H, 2H-tridecafluoro-n-octyl silane.
3. The preparation method according to claim 1, wherein the number of the circular arc grooves is plural, and the plural circular arc grooves are arranged in an array.
4. The preparation method according to claim 1 or 2, wherein the evaporation temperature is 80-120 ℃; the time of evaporation is 1-3 h.
5. The super-hydrophobic automatic positioning SERS spectrum detection platform prepared by the preparation method of any one of claims 1 to 4 comprises a substrate and super-hydrophobic arc-shaped grooves arranged on the surface of the substrate, wherein the contact angle of the super-hydrophobic arc-shaped grooves ranges from 153 degrees to 163 degrees.
6. The application of the superhydrophobic self-positioning SERS spectral detection platform in surface-enhanced Raman spectroscopy detection according to claim 5.
7. A surface-enhanced Raman spectroscopy detection method is characterized by comprising the following steps:
mixing the noble metal nano sol with the analyte sample solution, dropwise adding the obtained mixed solution into the super-hydrophobic arc-shaped groove of the super-hydrophobic automatic positioning SERS spectrum detection platform in claim 5, sequentially incubating and drying, and performing surface enhanced Raman spectrum detection.
8. The method of claim 7, wherein the analyte sample in the analyte sample solution comprises an environmental contaminant or a biomarker.
9. The method according to claim 7, wherein the noble metal nanosol comprises silver nanosol or gold nanosol.
10. The surface-enhanced Raman spectroscopy detection method according to claim 7, wherein the volume ratio of the noble metal nanosol to the analyte sample solution is 1-5: 1; the concentration of the noble metal nano sol is 100-600 nmol/L; the concentration of the analyte sample solution is greater than 10-13mol/L。
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